CN108409922A - A kind of graft copolymer and its preparation method and application containing reactive group - Google Patents
A kind of graft copolymer and its preparation method and application containing reactive group Download PDFInfo
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- CN108409922A CN108409922A CN201810144912.4A CN201810144912A CN108409922A CN 108409922 A CN108409922 A CN 108409922A CN 201810144912 A CN201810144912 A CN 201810144912A CN 108409922 A CN108409922 A CN 108409922A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention discloses a kind of graft copolymer and its preparation method and application containing reactive group.The graft copolymer is a kind of polymer of the side chain containing reactive group and polystyrene acrylate and its derivative segment, is copolymerized by free radical polymerization by the high molecular polymer C of monomer A, 5wt% ~ 30wt% of 40wt% ~ 90wt% carbon-carbon double bonds unsaturated monomer B, 5wt% containing reactive group ~ 30wt% carbon-carbon double bonds.Graft copolymer containing reactive group prepared by the present invention can improve glass fibre filling ABS material or the intensity of abs polymer alloy, the reactive group of high-content, which can improve the polystyrene acrylate introduced with the binding force of polymer or glass fiber material containing reactive group, side chain and its derivative segment, can improve the binding force with abs polymer.Compared with the graft copolymer of high grafting rate line style and comb-type structure that the prior art obtains, the intensity of material can be preferably improved in the case of similar molecular weight and reactive group content.
Description
Technical field
The present invention relates to the synthesis of graft copolymer and application fields, and in particular to a kind of grafting containing reactive group is total
Polymers and its preparation method and application.
Background technology
Acrylic nitrile-butadiene-styrene（ABS）With good physical and mechanical property, wear-resisting, oil resistant, corrosion-resistant, ruler
Very little stabilization, processing performance are preferable, are widely used in the fields such as household electrical appliances, automobile, electronic apparatus and building materials.Although ABS has good
Good comprehensive mechanical property, but its in intensity, heat resistance and solvent resistance etc., there is also deficiencies, interfere it further to answer
With ABS and different component are compounded, the comprehensive performance of ABS is can effectively improve.Glass fibre is introduced such as in ABS prepares glass
The material of fibre filling, can effectively improve the intensity and heat resistance of ABS products.And by ABS and polyamide（PA）It is compound, preparation
Alloy material has good solvent resistance.But it is by simple blending method that ABS is compound often right with other components
The performance of material improves unobvious, and the performance of material even declines after blending, it is therefore necessary to be carried by the way that third component is added
Its high intensity.
Glass fibre filling material or polymer alloy can be improved by adding some graft copolymers containing reactive group
Intensity.102746468 A of Chinese patent CN have found acrylic acid-grafted ethylene-octene block copolymer（OBC-g-AA）Plus
Polyethylene terephthalate can be improved by entering（PET）With ethylene-octene block copolymer（OBC）The tensile strength of alloy,
Notch impact strength and elongation at break.1702116 A of Chinese patent CN are prepared for using the method for fusion-grafting containing Malaysia
The ABS graft copolymer of anhydride group, and be applied to and prepare ABS and PA alloys.The result shows that being added to containing reactive base
The tensile strength and notch impact strength of the ABS/PA alloys of the ABS graft copolymer of group are improved.Styrene is added to connect
Branch maleic anhydride（SMA）The tensile strength, bending strength and notch shock that can effectively improve glass fibre filling polystyrene are strong
Degree（Zhang Daohai, He Min, Guo Jianbing, wait macromolecule journals, and 2014,3: 378-383.）.Chinese invention patent CN
The preparation method and its application in glass fibre filling polyester that 102558101 A disclose a kind of epoxide, epoxy compound
The introducing of object improves glass fibre filling polybutylene terephthalate (PBT)（PBT）Tensile strength and notch impact strength.China
101555341 A of patent CN have found, are added to intensity, toughness, the heat resistance of epoxy resin and the glass fibre filling ABS material of SMA
It can be improved with mobility.But the method that the graft copolymer containing reactive group mostly uses frit reaction extrusion,
Grafting functional group on polymer molecular chain, production technology is simpler, but since technique limits, single varieties, and grafting rate is low.
Additive amount is larger in actual use, and efficiency is low, and therefore, the graft copolymer that fusion-grafting method obtains tends not to meet real
Border demand.
In order to realize that effective control to product structure and grafting rate, 101851321 B of Chinese patent CN are poly- using suspending
The technique of conjunction is prepared for terpolymer styrene-acrylonitrile-glycidyl methacrylate（SAG）, can by this method
To control the content of epoxy group, the grafting rate of epoxy group is up to 10%.Therefore, height can be obtained by way of copolymerization to connect
The graft copolymer of branch rate.On this basis, 103421154 A of Chinese patent CN disclose a kind of comb containing reactive group
Type graft copolymer and its preparation method and application.Compared with the line style graft copolymer of commercialization, which can have
Effect improves modulus, elongation at break, yield strength and the tensile strength etc. of PET/ABS alloys（WY Dong, HT Wang, MF
He, et al. Industrial & Engineering Chemistry Research, 2015, 54: 2081-2089）.
Nevertheless, the polymer segment of side chain is mainly the homopolymerization of methyl acrylic ester or acrylic ester monomer in the patent
Object is not suitable for abs polymer system, and using Polystyrene-acrylate and its derivative segment as polymer lateral chain, it can
To improve the binding force of abs polymer, the alloy product haveing excellent performance is obtained.
Invention content
The primary purpose of the present invention is that low for existing glass fibre filling material and polymer blend alloy mechanical strength
Disadvantage provides a kind of new and effective graft copolymer containing reactive group.
Another object of the present invention is to provide the preparation methods of the above-mentioned graft copolymer containing reactive group.
The object of the invention is achieved through the following technical solutions：
A kind of graft copolymer containing reactive group, the graft copolymer are that side chain contains reactive group and polystyrene-
A kind of polymer of acrylate and its derivative segment is made by following substance reaction by weight percentage：
The monomer A of 40wt% ~ 90wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 30wt% containing reactive group；
The high molecular polymer C of 5wt% ~ 30wt% carbon-carbon double bonds；
The graft copolymer number-average molecular weight containing reactive group is 10000 ~ 110000, preferably 11000 ~ 48000, weight
Average molecular weight is 33000 ~ 210000, preferably 36000 ~ 98000.
The present invention utilizes the high molecular polymer C of carbon-carbon double bonds and the monomer A of carbon-carbon double bonds, containing reactive group
Graft copolymer of the side chain containing reactive group and high molecular polymer is obtained by the reaction in unsaturated monomer B.The reactivity of high-content
Group can improve with the binding force of polymer or glass containing reactive group, and in the present invention carbon-carbon double bonds macromolecule
After polymer C copolymerization, Polystyrene-acrylate and its derivative segment are introduced into side chain, the alternate knot with ABS's can be improved
With joint efforts.The high grafting rate line style and combed knot that graft copolymer containing reactive group prepared by the present invention is obtained with the prior art
The graft copolymer of structure is compared, and glass fibre filling can be more effectively improved in the case of close molecular weight and reactive group content
The intensity of ABS material and abs polymer alloy.
It is further preferred that the graft copolymer containing reactive group, by weight percentage, anti-by following substance
It should be made：
The monomer A of 60wt% ~ 85wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 20wt% containing reactive group；
The high molecular polymer C of 10wt% ~ 20wt% carbon-carbon double bonds.
The high molecular polymer C of the carbon-carbon double bonds is reacted with the monomer E of carbon-carbon double bonds by high molecular polymer D
It obtains, wherein the high molecular polymer D chemical general formulas are：
Wherein R1For hydrogen atom, methyl or ethyl, R2For hydrogen atom or methyl, R3For methyl, ethyl, butyl, isobutyl group, octyl
Or iso-octyl；The integer that m is 20 ~ 120, the integer that n is 10 ~ 150, the integer that k is 1 ~ 99, the integer that p is 2 ~ 12；S is that sulphur is former
Son, G are reactive groups, are carboxyl, amino or hydroxyl；
The monomer E of the carbon-carbon double bonds carries epoxy group, amino, isocyanate group or acid chloride group.
Preferably, the monomer E of the carbon-carbon double bonds is selected from acrylamide, Methacrylamide, Glycidyl methacrylate
Glyceride, allyl glycidyl ether, acryloyl chloride, methacrylic chloride, methylacryoyloxyethyl isocyanates and its spread out
One or more of biology.
Preferably, the high molecular polymer C number-average molecular weights of the carbon-carbon double bonds are 3000 ~ 13000.
Preferably, the monomer A of the carbon-carbon double bonds is selected from methyl methacrylate, ethyl methacrylate, methyl-prop
Olefin(e) acid butyl ester, isooctyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, benzene second
It is one or more of in alkene, α-methylstyrene, α-ethyl styrene, acrylonitrile, methacrylonitrile and its derivative.
Preferably, the unsaturated monomer B containing reactive group is selected from unsaturated acid anhydride, carboxylic acid, isocyanates, hydroxyl
One or more of ester, amide, oxazolines, siloxanes and its derivative, it is specific such as maleic anhydride, alkenyl succinic anhydride
Derivative, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, acrylic acid, first
Base acrylic acid, itaconic acid, N hydroxymethyl acrylamide, acrylamide, Methacrylamide, 2- ethylene -2- oxazolines, γ-first
Base acryloyloxypropyltrimethoxysilane, isocyanatoethyl, 3- isopropyls-dimethyl benzyl isocyanic acid
Ester, isocyanates ethyl acrylate etc..
The viscous state temperature of graft copolymer of the present invention containing reactive group is 130 DEG C ~ 200 DEG C, preferably
140℃~180℃.It is unfavorable for the melt blending of graft copolymer when viscous state temperature being less than 130 DEG C or higher than 200 DEG C.
The present invention also provides the preparation methods of the above-mentioned graft copolymer containing reactive group, include the following steps：
By the high molecular polymer C of the monomer A of carbon-carbon double bonds, unsaturated monomer B and carbon-carbon double bonds containing reactive group
It is copolymerized by free radical polymerisation process.
The free radical polymerisation process is bulk polymerization, polymerisation in solution, suspension polymerisation or emulsion polymerization, is that this field is normal
The preparation method of rule, the specific method is as follows：
The bulk polymerization preparation method is：By the monomer A of carbon-carbon double bonds, the unsaturated monomer B containing reactive group and contain
The high molecular polymer C and initiator of carbon-carbon double bond slowly heat up after mixing, after reacting 1 ~ 10h at 40 DEG C ~ 100 DEG C,
The graft copolymer containing reactive group is obtained after drying.
The polymerisation in solution preparation method is：By the monomer A of carbon-carbon double bonds, the unsaturated monomer B containing reactive group,
High molecular polymer C, organic solvent and the initiator of carbon-carbon double bonds slowly heat up after mixing, anti-at 40 DEG C ~ 100 DEG C
After answering 1 ~ 10h, the graft copolymer containing reactive group is obtained after devolatilization drying.
The suspension polymerization preparation method is：By the monomer A of carbon-carbon double bonds, the unsaturated monomer B containing reactive group,
High molecular polymer C, water, dispersant and the initiator of carbon-carbon double bonds slowly heat up after mixing, at 40 DEG C ~ 100 DEG C
After reacting 1 ~ 10h, the graft copolymer containing reactive group is obtained after filtration drying.
The emulsion-polymerizing preparation method is：By the monomer A of carbon-carbon double bonds, the unsaturated monomer B containing reactive group,
High molecular polymer C, water, emulsifier and the initiator of carbon-carbon double bonds slowly heat up after mixing, at 40 DEG C ~ 100 DEG C
After reacting 1 ~ 10h, the graft copolymer containing reactive group is obtained after dry.
Wherein, when unsaturated monomer B whens containing isocyanate groups, the free radical polymerisation process is bulk polymerization or solution
One kind in polymerization.
Wherein, the preparation method of the high molecular polymer C of the carbon-carbon double bonds, includes the following steps：
Under the conditions of existing for chain-transferring agent, by one in styrene, α-methylstyrene, α-ethyl styrene and its derivative
Kind or several and methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate, propylene
One or more of sour methyl esters, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer cause radical polymerization by initiator
It closes and high molecular polymer D is made；Then obtained high molecular polymer D is reacted at room temperature with the monomer E of carbon-carbon double bonds,
Obtain the high molecular polymer C of carbon-carbon double bonds.
The molar ratio of the high molecular polymer D and the monomer E of carbon-carbon double bonds are 1:0.8~1.3.
The chain-transferring agent is one or more of the aliphatic mercaptan containing carboxyl, hydroxyl or amino, specific such as mercapto
Base propyl alcohol, mercaptoethanol, sulfydryls hexanol, mercaptoundecanol, thioacetic acid, mercaptopropionic acid, dimercaptosuccinic acid, mercaptohexanoic acid, mercapto
Base hendecanoic acid, sulfydryl lauric acid/dodecanoic acid, mercaptoethylmaine, 3- sulfydryl -1- propylamine etc..
The initiator is one kind or several in azo-initiator, peroxide initiator or redox initiator
Kind, it is specific such as azodiisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, azo-bis-iso-dimethyl, two hexamethylene of azo
Base formonitrile HCN, azo-bis-isobutyrate hydrochloride, azo dicyano valeric acid, lauroyl peroxide, benzoyl peroxide, hydrogen peroxide are different
Propyl benzene, tert-butyl hydroperoxide, di-cyclohexylperoxy di-carbonate, potassium peroxydisulfate, ammonium persulfate, (NH4)2S2O8-FeSO4、It crosses
Aoxidize dibenzoyl-N, N dimethyl aniline, ammonium persulfate-sodium bisulfite etc..
Catalyst and inhibition can be according to circumstances added when being reacted with the monomer E of carbon-carbon double bonds in high molecular polymer D in right amount
Agent, the catalyst are tertiary amine catalyst, specific such as N, N- dimethyl benzylamines, triethylamine, N, N- dimethyl cyclohexyl amines, double
(2- dimethylaminoethyls) ether, n-ethylpiperazine etc..
The polymerization inhibitor is radical polymerization inhibitor, specific such as hydroquinone, p-tert-Butylcatechol, methylnaphthohydroquinone, sulphur
Diphenylamines, nitrosobenzene, m-dinitrobenzene, 1,4-benzoquinone, p-hydroxyanisole, stannous chloride, ferric trichloride, phosphorous triphenyl phosphate
Ester etc..
Graft copolymer of the present invention containing reactive group can be the particle made by pelleter, comminutor,
It can be the powder that pulverizer makes.
The present invention also provides the above-mentioned graft copolymers containing reactive group to improve glass fibre filling ABS material or ABS
Application in the intensity of polymer alloy.
The present invention also provides a kind of ABS resin composition, including the above-mentioned graft copolymer containing reactive group and
ABS resin.
Compared with prior art, the present invention has the advantages that：
Graft copolymer containing reactive group prepared by the present invention can improve glass fibre filling ABS material or abs polymer closes
The reactive group of the intensity of gold, high-content can improve and the binding force of polymer or glass fiber material containing reactive group,
The Polystyrene-acrylate and its derivative segment that side chain introduces can improve the binding force with abs polymer.With the prior art
The high grafting rate line style obtained is compared with the graft copolymer of comb-type structure, in similar molecular weight and reactive group content
In the case of can preferably improve the intensity of material.
Specific implementation mode
Explanation is further expalined to the present invention with reference to specific embodiment, the description thereof is more specific and detailed, but
It cannot be construed as a limitation to the scope of the present invention, as long as the form using equivalent substitution or equivalent transformation is obtained
The technical solution obtained, should all be included within the protection domain of the claims in the present invention.
In following embodiment, raw material used is commercial goods.
Test and characterizing method
（One）Examination of infrared spectrum
Tabletting after the graft copolymer containing reactive group of acquisition is milled with the potassium bromide after drying, is placed on Fourier change
Infrared spectrometer is changed to be tested.4000 ~ 400cm of scanning range-1, resolution ratio 4cm-1, scanning times 16 times.
（Two）Gel permeation chromatography（GPC）Test
After the graft copolymer containing reactive group of acquisition is dissolved with tetrahydrofuran, measured using gel permeation chromatograph poly-
The retention time of object is closed, detecting instrument is refraction index analyzer, and mobile phase is tetrahydrofuran, is made using monodisperse polystyrene
The weight average molecular weight and number-average molecular weight of polymer are calculated for standard specimen.
（Three）Viscous state temperature test
By the graft copolymer containing reactive group of acquisition after heating melts, the thin slice that thickness is about 2mm is made, and adopt
Use thermomechanical analyzer（TMA）The temperature strain curve for testing copolymer obtains the viscous of copolymer according to temperature strain curve
Fluidised form temperature.
Embodiment 1
Under nitrogen protection, by 75g styrene, 25g methyl methacrylates, 1.5g chain-transferring agents mercaprol, 4.0g initiators
After azodiisobutyronitrile and 200g solvent toluenes are mixed evenly, four mouthfuls equipped with agitating paddle, condenser and thermometer are moved to
In bottle, 65 DEG C are heated to, after reacting 6h, obtains the toluene solution of pbz polymer polymer D；Reaction system is down to room temperature, is added
Enter 0.01g hydroquinone of polymerization retarder, 0.04g catalyst ns, the monomer E methyl-props of N- dimethyl benzylamines and 2.1g carbon-carbon double bonds
Alkene acyl chlorides（The monomer E molar ratios of high molecular polymer D and carbon-carbon double bonds are 1:1.2）, after reaction 8h is stirred at room temperature, by product
After revolving is dry, the high molecular polymer C of carbon-carbon double bonds is obtained, understands obtained high molecular polymer C's by GPC tests
Number-average molecular weight is about 5340.
Under nitrogen protection, by 90g styrene, 30g methyl methacrylates, 20g glycidyl methacrylate, 10g
High molecular polymer C, 4.2g azodiisobutyronitrile and 150g ethyl acetate of the carbon-carbon double bonds of above-mentioned preparation are mixed equal
After even（The high molecular polymer C use of the monomer A of carbon-carbon double bonds, unsaturated monomer B and carbon-carbon double bonds containing reactive group
Amount is respectively 80.00wt%, 13.33wt% and 6.67wt%）, it moves in the four-hole bottle equipped with agitating paddle, condenser and thermometer,
75 DEG C are heated to, after reacting 6h, after product revolving drying, obtains graft copolymer.By infrared spectrum it is found that obtained grafting
Copolymer contains epoxy group；It is tested by GPC, graft copolymer number-average molecular weight of the gained containing epoxy group is about 26920,
Weight average molecular weight is 51300；The viscous state temperature of graft copolymer of the gained containing epoxy group is about 170 DEG C.
Embodiment 2
Under nitrogen protection, by 100g styrene, 25g methyl acrylates, 1.8g chain-transferring agents mercaprol, 2.7g initiator azos
After bis-isobutyronitrile and 200g solvent toluenes are mixed evenly, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer,
65 DEG C are heated to, after reacting 6h, obtains the toluene solution of pbz polymer polymer D；Reaction system is down to room temperature, is added
The monomer E methacrylic chlorides of 0.01g polymerization inhibitors phenothiazine, 0.02g catalyst of triethylamine and 1.84g carbon-carbon double bonds
（The monomer E molar ratios of high molecular polymer D and carbon-carbon double bonds are 1:0.9）, after reaction 8h is stirred at room temperature, product is rotated dry
After dry, the high molecular polymer C of carbon-carbon double bonds is obtained, is divided equally by the number of the high molecular polymer C obtained known to GPC tests
Son amount about 7640.
It is under nitrogen protection, 80g styrene, 20g butyl acrylates, 40g glycidyl methacrylate, 10g is above-mentioned
After high molecular polymer C, 3.0g azodiisobutyronitrile and 150g toluene of the carbon-carbon double bonds of preparation are mixed evenly（It is carbon containing
The monomer A of carbon double bond, unsaturated monomer B and carbon-carbon double bonds containing reactive group high molecular polymer C dosages be respectively
66.67wt%, 26.67wt% and 6.66wt%）, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to 75
DEG C, after reacting 6h, after product revolving drying, obtain graft copolymer.By infrared spectrum it is found that obtained graft copolymer contains
There is epoxy group；It is tested by GPC, graft copolymer number-average molecular weight of the gained containing epoxy group is about 43900, Weight-average molecular
Amount is 81200；The viscous state temperature of graft copolymer of the gained containing epoxy group is about 167 DEG C.
Embodiment 3
Under nitrogen protection, 70g α-methylstyrenes, 50g butyl acrylates, 1.5g chain-transferring agents mercaprol, 3.5g are drawn
After hair agent azodiisobutyronitrile and 240g solvent xylenes are mixed evenly, move to equipped with agitating paddle, condenser and thermometer
Four-hole bottle in, be heated to 65 DEG C, after reacting 6h, obtain the xylene solution of pbz polymer polymer D；Reaction system is down to
0.01g polymerization inhibitors nitrosobenzene, 0.02g catalyst ns, the list of N- dimethyl cyclohexyl amines and 1.36g carbon-carbon double bonds is added in room temperature
Body E methacrylic chlorides（The monomer E molar ratios of high molecular polymer D and carbon-carbon double bonds are 1:0.8）, reaction 5h is stirred at room temperature
Afterwards, by after product revolving drying, the high molecular polymer C of carbon-carbon double bonds is obtained.Pass through the macromolecule obtained known to GPC tests
The number-average molecular weight of polymer C is about 6110.
It, will be on 110g α-methylstyrenes, 20g Isooctyl acrylate monomers, 16g hydroxy-ethyl acrylates, 54g under nitrogen protection
High molecular polymer C, 2.2g azodiisobutyronitrile and 300g butyl acetates for stating the carbon-carbon double bonds of preparation are mixed evenly
Afterwards（The high molecular polymer C dosages of the monomer A of carbon-carbon double bonds, unsaturated monomer B and carbon-carbon double bonds containing reactive group
Respectively 65.00wt%, 8.00wt% and 27.00wt%）, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, add
Heat is to 75 DEG C, after reacting 6h, after product revolving drying, obtains graft copolymer.By infrared spectrum it is found that obtained grafting is total to
Polymers contains hydroxyl group；It is tested by GPC, the graft copolymer number-average molecular weight of gained hydroxyl group is about 38700, weight
Average molecular weight is 71600；The viscous state temperature of the graft copolymer of gained hydroxyl group is about 159 DEG C.
Embodiment 4
Under nitrogen protection, by 80g styrene, 40g ethyl acrylates, 2g chain-transferring agents mercaptoethanol, 1.5g initiators azo two
After different heptonitrile and 120g solvent ethyl acetates are mixed evenly, the four-hole bottle equipped with agitating paddle, condenser and thermometer is moved to
In, 70 DEG C are heated to, after reacting 5h, obtains the ethyl acetate solution of pbz polymer polymer D；Reaction system is down to room temperature,
The monomer E methacrylic acids of 0.01g polymerization inhibitors 1,4-benzoquinone, 0.02g catalyst ns-ethyl piperazidine and 5.0g carbon-carbon double bonds are added
Isocyano group ethyl ester（The monomer E molar ratios of high molecular polymer D and carbon-carbon double bonds are 1:1.25）, after reaction 10h is stirred at room temperature,
After product revolving drying, the high molecular polymer C of carbon-carbon double bonds is obtained.Pass through the polyphosphazene polymer obtained known to GPC tests
The number-average molecular weight for closing object C is about 12970.
It, will be on 80g α-ethyl styrene, 40g butyl acrylates, 15g 2- ethylene -2- oxazolines, 15g under nitrogen protection
State high molecular polymer C, 1.6g benzoyl peroxide of the carbon-carbon double bonds of preparation and after 150g toluene is mixed evenly（Contain
The high molecular polymer C dosages difference of the monomer A of carbon-carbon double bond, unsaturated monomer B and carbon-carbon double bonds containing reactive group
For 80.00wt%, 10.00wt% and 10.00wt%）, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to
80 DEG C, after reacting 8h, after product revolving drying, obtain graft copolymer.By infrared spectrum it is found that obtained graft copolymer
Containing there is oxazoline group；It is tested by GPC, the graft copolymer number-average molecular weight of gained group containing oxazoline is about 52200, weight
Average molecular weight is 87900；The viscous state temperature of the graft copolymer of gained group containing oxazoline is about 165 DEG C.
Embodiment 5
Under nitrogen protection, 95g α-ethyl styrene, 5g methyl methacrylates, 2g chain-transferring agents thioacetic acid, 1.5g are drawn
After hair agent azobisisoheptonitrile and 180g solvent xylenes are mixed evenly, move to equipped with agitating paddle, condenser and thermometer
Four-hole bottle in, be heated to 70 DEG C, after reacting 5h, obtain the xylene solution of pbz polymer polymer D；It is down to room temperature, is added
The monomer E Glycidyl methacrylates of 0.01g hydroquinone of polymerization retarder, 0.02g catalyst of triethylamine and 4.0g carbon-carbon double bonds are sweet
Grease（The monomer E molar ratios of high molecular polymer D and carbon-carbon double bonds are 1:1.3）, be warming up to 130 DEG C be stirred to react 12h after,
After product revolving drying, the high molecular polymer C of carbon-carbon double bonds is obtained.Pass through the polyphosphazene polymer obtained known to GPC tests
The number-average molecular weight for closing object C is about 10610.
Under nitrogen protection, by 70g α-methylstyrenes, 20g methyl methacrylates, 5g γ-methacryloxy third
High molecular polymer C, 1.5g azodiisobutyronitrile and 100g first of the carbon-carbon double bonds of the above-mentioned preparation of base trimethoxy silane, 5g
After benzene is mixed evenly（The height of the monomer A of carbon-carbon double bonds, unsaturated monomer B and carbon-carbon double bonds containing reactive group
Molecularly Imprinted Polymer C dosages are respectively 90.00wt%, 5.00wt% and 5.00wt%）, move to equipped with agitating paddle, condenser and thermometer
Four-hole bottle in, be heated to 75 DEG C, after reacting 8h, by product revolving it is dry after, obtain graft copolymer.It can by infrared spectrum
Know, obtained graft copolymer contains siloxane group；It is tested by GPC, the graft copolymer number of gained silicone-containing group
Average molecular weight is about 47400, weight average molecular weight 89600；The viscous state temperature of the graft copolymer of gained silicone-containing group
About 189 DEG C.
Embodiment 6
Under nitrogen protection, by 5g styrene, 95g methyl methacrylates, 2g chain-transferring agents thioacetic acid, 1.8g initiator azos
After two different heptonitriles and 120g solvent acetic acid butyl esters are mixed evenly, four mouthfuls equipped with agitating paddle, condenser and thermometer are moved to
In bottle, 70 DEG C are heated to, after reacting 5h, obtains the butyl acetate solution of pbz polymer polymer D；It is down to room temperature, 0.01g is added
The monomer E metering systems of polymerization inhibitor stannous chloride, 0.02g catalyst bis- (2- dimethylaminoethyls) ethers and 2.4g carbon-carbon double bonds
Acid glycidyl ester（The monomer E molar ratios of high molecular polymer D and carbon-carbon double bonds are 1:0.8）, it is anti-to be warming up to 130 DEG C of stirrings
After answering 12h, after product revolving drying, the high molecular polymer C of carbon-carbon double bonds is obtained.Pass through what is obtained known to GPC tests
The number-average molecular weight of high molecular polymer C is about 12300.
Under nitrogen protection, by 5g styrene, 95g methyl methacrylates, 60g maleic anhydrides, 40g above-mentioned preparations
After high molecular polymer C, 1.5g benzoyl peroxide and 300g butyl acetates of carbon-carbon double bonds are mixed evenly（Carbon containing carbon
The monomer A of double bond, unsaturated monomer B and carbon-carbon double bonds containing reactive group high molecular polymer C dosages be respectively
50.00wt%, 30.00wt% and 20.00wt%）, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to 85
DEG C, after reacting 8h, after product revolving drying, obtain graft copolymer.By infrared spectrum it is found that obtained graft copolymer contains
There is anhydride group；It is tested by GPC, graft copolymer number-average molecular weight of the gained containing anhydride group is about 67400, Weight-average molecular
Amount is 108800；The viscous state temperature of graft copolymer of the gained containing anhydride group is about 183 DEG C.
Embodiment 7
Under nitrogen protection, by 50g α-methylstyrenes, 50g 2-ethyl hexyl acrylates, 2.4g mercaptoethylmaines, 4.8g azobisisovaleronitrile
After being mixed evenly with 280g ethyl acetate, moves in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to 65
DEG C, after reacting 7h, obtain the ethyl acetate solution of pbz polymer polymer D；It is down to room temperature, 0.02g polymerization inhibitors are added to benzene two
The monomer E isocyanatoethyls of phenol and 4.8g carbon-carbon double bonds（The monomer of high molecular polymer D and carbon-carbon double bonds
E molar ratios are 1:1）, after reaction 8h is stirred at room temperature, after product revolving drying, obtain the high molecular polymer of carbon-carbon double bonds
C.Number-average molecular weight by the high molecular polymer C obtained known to GPC tests is about 3100.
Under nitrogen protection, by 30g styrene, 50g butyl methacrylates, 10g isocyanatoethyls, 10g
After high molecular polymer C, 4.8g azodiisobutyronitrile and 280g toluene of the carbon-carbon double bonds of above-mentioned preparation are mixed evenly
（The high molecular polymer C dosages point of the monomer A of carbon-carbon double bonds, unsaturated monomer B and carbon-carbon double bonds containing reactive group
It Wei not 80.00wt%, 10.00wt% and 10.00wt%）, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, heat
To 75 DEG C, after reacting 6h, after product revolving drying, graft copolymer is obtained.By infrared spectrum it is found that obtained graft copolymerization
Object contains isocyanate groups；It is tested by GPC, graft copolymer number-average molecular weight of the gained containing isocyanate groups is about
10800, weight average molecular weight 31500；The viscous state temperature of graft copolymer of the gained containing isocyanate groups is about 131 DEG C.
Embodiment 8
It is under nitrogen protection, 80g α-methylstyrenes, 20g isobutyl acrylates, 2.4g sulfydryls lauric acid/dodecanoic acid, 2.4g azos two is different
After butyronitrile and 150g toluene are mixed evenly, move in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to 70
DEG C, after reacting 5h, obtain the toluene solution of pbz polymer polymer D；0.02g hydroquinone of polymerization retarder and the carbon containing carbon of 1.6g is added
The monomer E dimethylamino-propyl Methacrylamides of double bond（The monomer E molar ratios of high molecular polymer D and carbon-carbon double bonds are
1:1）, after being stirred to react 8h, after product revolving drying, obtain the high molecular polymer C of carbon-carbon double bonds.It is tested by GPC
Understand that the number-average molecular weight of obtained high molecular polymer C is about 8020.
By 98g methyl methacrylates, 10g acrylamides, the above-mentioned preparations of 12g carbon-carbon double bonds high molecular polymer
C, 2.4 g anion emulsifiers lauryl sodium sulfate, 1.2g nonionic emulsifier polyoxethylene octylphenyls phenol ether, 1.0g cause
Homogenizer high-speed stirred 15min is used after agent potassium peroxydisulfate and the mixing of 175g distilled water, obtains pre-emulsion（Carbon-carbon double
The monomer A of key, unsaturated monomer B and carbon-carbon double bonds containing reactive group high molecular polymer C dosages be respectively
81.67wt%, 8.33wt% and 10.00wt%）；The pre-emulsion of acquisition is moved to four equipped with agitating paddle, condenser and thermometer
In mouth bottle, nitrogen atmosphere protection is heated to 75 DEG C, after reacting 8h, is cooled to room temperature, the CaCl of 10 ml a concentration of 5% is added2Water
Solution, demulsification are washed product repeatedly with distilled water after precipitating, and are crushed after then drying, are obtained graft copolymer.By infrared light
Spectrum is it is found that obtained graft copolymer contains amine groups；It is tested by GPC, the graft copolymer number of gained amino-contained group
Average molecular weight is about 77600, weight average molecular weight 159800；The viscous state temperature of the graft copolymer of gained amino-contained group is about
It is 196 DEG C.
Embodiment 9
Under nitrogen protection, by 20g styrene, 80g methyl methacrylates, 2.4g mercaptoethylmaines, 3.6g azobisisovaleronitrile and
It after 250g toluene is mixed evenly, moves in the four-hole bottle equipped with agitating paddle, condenser and thermometer, is heated to 65 DEG C, instead
After answering 7h, it is down to room temperature, obtains the toluene solution of pbz polymer polymer D；0.02g hydroquinone of polymerization retarder is added and 4.8g contains
The monomer E isocyanatoethyls of carbon-carbon double bond（The monomer E molar ratios of high molecular polymer D and carbon-carbon double bonds are
1:1）, after reaction 8h is stirred at room temperature, after product revolving drying, obtain the high molecular polymer C of carbon-carbon double bonds.Pass through GPC
The number-average molecular weight of the high molecular polymer C obtained known to test is about 6940.
2g calcium phosphate and 2g sodium sulphate are dissolved in 150g distilled water, moved to equipped with agitating paddle, condenser and thermometer
Four-hole bottle in；By 80g styrene, 10g methacrylic acids, 1.4g initiators (NH4)2S2O8-FeSO4, 30g above-mentioned preparations contain
The high molecular polymer C of carbon-carbon double bond is after mixing（The monomer A of carbon-carbon double bonds, the unsaturated monomer B containing reactive group
High molecular polymer C dosages with carbon-carbon double bonds are respectively 66.67wt%, 8.33wt% and 25.00wt%）, it is added above-mentioned four mouthfuls
In bottle, nitrogen atmosphere protection is heated to 65 DEG C, after reacting 7h, product is washed and is filtered, graft copolymer is obtained after dry.By
Infrared spectrum is it is found that obtained graft copolymer contains carboxylic group；It is tested by GPC, the grafting of gained carboxyl group is total
Polymers number-average molecular weight is about 96700, weight average molecular weight 198300；The viscous state of the graft copolymer of gained carboxyl group
Temperature is about 200 DEG C.
Embodiment 10
Under nitrogen protection, by 75g styrene, 25g methyl methacrylates, 1.5g chain-transferring agents mercaprol, 2.0g initiators
After azodiisobutyronitrile and 150g solvent toluenes are mixed evenly, four mouthfuls equipped with agitating paddle, condenser and thermometer are moved to
In bottle, 65 DEG C are heated to, after reacting 6h, obtains the toluene solution of pbz polymer polymer D；Reaction system is down to room temperature, is added
Enter 0.01g hydroquinone of polymerization retarder, 0.04g catalyst ns, the monomer E methyl-props of N- dimethyl benzylamines and 2.1g carbon-carbon double bonds
Alkene acyl chlorides（The monomer E molar ratios of high molecular polymer D and carbon-carbon double bonds are 1:1.2）, after reaction 8h is stirred at room temperature, by product
After revolving is dry, the high molecular polymer C of carbon-carbon double bonds is obtained, understands obtained high molecular polymer C's by GPC tests
Number-average molecular weight is about 12340.
Under nitrogen protection, by 90g styrene, 30g methyl methacrylates, 20g glycidyl methacrylate, 10g
High molecular polymer C, 1.5g azodiisobutyronitrile and 120g ethyl acetate of the carbon-carbon double bonds of above-mentioned preparation are mixed equal
After even（The high molecular polymer C use of the monomer A of carbon-carbon double bonds, unsaturated monomer B and carbon-carbon double bonds containing reactive group
Amount is respectively 80.00wt%, 13.33wt% and 6.67wt%）, it moves in the four-hole bottle equipped with agitating paddle, condenser and thermometer,
75 DEG C are heated to, after reacting 6h, after product revolving drying, obtains graft copolymer.By infrared spectrum it is found that obtained grafting
Copolymer contains epoxy group；It is tested by GPC, graft copolymer number-average molecular weight of the gained containing epoxy group is about 61810,
Weight average molecular weight is 112300；The viscous state temperature of graft copolymer of the gained containing epoxy group is about 198 DEG C.
Comparative example 1
Under nitrogen protection, 90g styrene, 30g methyl methacrylates, 20g glycidyl methacrylate, 1.8g are drawn
After hair agent azodiisobutyronitrile and 180g solvent ethyl acetates are mixed evenly, move to equipped with agitating paddle, condenser and temperature
In the four-hole bottle of meter, 75 DEG C are heated to, after reacting 6h, is down to room temperature, after product revolving drying, obtains linear copolymers.By
Infrared spectrum is it is found that obtained linear copolymers contain epoxy group；It is tested by GPC, line style of the gained containing epoxy group is total
Polymers number-average molecular weight is about 26320, weight average molecular weight 52400.
Comparative example 2
Under nitrogen protection, by 100g methyl methacrylates, 3.2g chain-transferring agents thioacetic acid, 3g initiator azodiisobutyronitriles
After being mixed evenly with 200g solvent toluenes, moves in the four-hole bottle equipped with agitating paddle, condenser and thermometer, be heated to 65
DEG C, after reacting 6h, it is down to room temperature, 0.01g hydroquinone of polymerization retarder, 0.04g catalyst of triethylamine and 5g methacrylic acids is added
Ethylene oxidic ester after 100 DEG C are stirred to react 10h, after product revolving drying, obtains the high molecular polymer C of carbon-carbon double bonds,
Number-average molecular weight by the high molecular polymer C obtained known to GPC tests is about 4100.
Under nitrogen protection, by 120g methyl methacrylates, 20g glycidyl methacrylate, 10g above-mentioned preparations
After high molecular polymer C, 1.5g azodiisobutyronitrile and 200g toluene of carbon-carbon double bonds are mixed evenly, move to be equipped with and stir
In the four-hole bottle for mixing paddle, condenser and thermometer, 75 DEG C are heated to, after reacting 6h, after product revolving drying, combed is obtained and connects
Graft copolymer.By infrared spectrum it is found that obtained comb-grafted copolymer contains epoxy group；It is tested by GPC, gained contains ring
The comb-grafted copolymer number-average molecular weight of oxygen groups is about 26110, weight average molecular weight 53200.
Application performance test
1. glass fibre filling material
The graft copolymer containing reactive group obtained in comparative example 1, comparative example 2 and embodiment 1-10 is applied to prepare and is contained
The ABS glass fibre filling materials of 10% glass, and compared with commercially available acid anhydrides type graft copolymer SMA.Wherein ABS glass fibre fillings material
Formula is 10 parts of glass, 88 parts of ABS, 2 parts of graft copolymer；Blank sample is 10 parts of glass, 90 parts of ABS.
Raw material A BS dries 4h in 80 DEG C of baking ovens, spare.Each material is uniformly mixed, double screw extruder spout is added
Extruding pelletization, glass using side feed mode, squeeze out material strip it is water cooled by sink, drying after be sent into pelleter pelletizing obtain ABS
Injection molding machine hopper is added in 80 DEG C of the Alloy plastic particle drying 4 hours of acquisition by glass fibre filling material, sets corresponding injection molding work
Skill, injection molding press mold are molded to obtain the standard batten of test.Notch impact strength is according to ISO 180-93 standard testings, amount of deflection root
According to ISO 178-93 standard testings, rate of bending is 2 mm/min, and test result is as shown in table 1.
The ABS glass fibre filling material properties of 1 10% glass of table
As shown in Table 1, glass fibre filling material notch impact strength and the amount of deflection for not adding graft copolymer are relatively low.Grafting is added altogether
Notch impact strength and amount of deflection improve after polymers.As can be seen that the effect of graft copolymer containing reactive group prepared by the present invention
Better than common acid anhydrides type graft copolymer SMA on the market at present；Embodiment 1 is compared with comparative example 1,2, in similar molecular weight
Under the conditions of anhydride group content, line style that the graft copolymer containing anhydride group prepared by the present invention is obtained than the prior art and
The graft copolymer of comb-type structure can preferably improve the intensity of material.
Polymer blend alloy
By the graft copolymer containing epoxy group obtained in comparative example 1, comparative example 2 and embodiment 1,2 be applied to prepare ABS with
Polyethylene terephthalate（PET）Alloy, and compared with Commercial epoxy type graft copolymer SAG.Wherein ABS/PET alloys
70 parts of ABS in formula, 28 parts of PET, 2 parts of graft copolymer；30 parts of 70 parts of blank sample ABS, PET.
Each material is uniformly mixed and double spiral shells is added by raw material A BS and PET respectively in 80 DEG C and 120 DEG C of baking ovens after dry 4h
Bar extruder feed port extruding pelletization, squeeze out material strip it is water cooled by sink, drying after be sent into pelleter pelletizing obtain ABS/PET
Injection molding machine hopper is added in 80 DEG C of the Alloy plastic particle drying 4 hours of acquisition by alloy, sets corresponding Shooting Technique, injection molding pressure
Film is molded to obtain the standard batten of test.Notch impact strength is according to 256 standard testings of ASTM D, test result such as 2 institute of table
Show.
2 ABS/PET alloy properties of table
As shown in Table 2, the ABS/PET alloy material notch impact strengths for not adding graft copolymer are relatively low, and graft copolymerization is added
The notch impact strength of alloy product increases after object.As can be seen that the effect of graft type copolymer containing epoxy group prepared by the present invention
Fruit is better than common epoxy type graft copolymer on the market at present；Embodiment 1 is compared with comparative example 1,2, in similar molecular weight
Under conditions of epoxy group content, the graft copolymer containing epoxy group prepared by the present invention is than the line style that the prior art obtains
The intensity of alloy can be preferably improved with the graft copolymer of comb-type structure.
Claims (14)
1. a kind of graft copolymer containing reactive group, which is characterized in that the graft copolymer is that side chain contains reactive base
A kind of polymer of group and Polystyrene-acrylate and its derivative segment, by weight percentage, by following substance reaction
It is made：
The monomer A of 40wt% ~ 90wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 30wt% containing reactive group；
The high molecular polymer C of 5wt% ~ 30wt% carbon-carbon double bonds；
The graft copolymer number-average molecular weight containing reactive group is 10000 ~ 110000, preferably 11000 ~ 48000, weight
Average molecular weight is 33000 ~ 210000, preferably 36000 ~ 98000.
2. the graft copolymer containing reactive group according to claim 1, which is characterized in that by weight percentage, by
Following substance reaction is made：
The monomer A of 60wt% ~ 85wt% carbon-carbon double bonds；
Unsaturated monomer Bs of the 5wt% ~ 20wt% containing reactive group；
The high molecular polymer C of 10wt% ~ 20wt% carbon-carbon double bonds.
3. the graft copolymer according to claim 1 or claim 2 containing reactive group, which is characterized in that the height of carbon-carbon double bonds
Molecularly Imprinted Polymer C is obtained by the reaction by the monomer E of high molecular polymer D and carbon-carbon double bonds, wherein the high molecular polymer
D chemical general formulas are：
Wherein R1For hydrogen atom, methyl or ethyl, R2For hydrogen atom or methyl, R3For methyl, ethyl, butyl, isobutyl group, octyl
Or iso-octyl；The integer that m is 20 ~ 120, the integer that n is 10 ~ 150, the integer that k is 1 ~ 99, the integer that p is 2 ~ 12；S is that sulphur is former
Son, G are reactive groups, are carboxyl, amino or hydroxyl；
The monomer E of the carbon-carbon double bonds carries epoxy group, amino, isocyanate group or acid chloride group.
4. the graft copolymer containing reactive group according to claim 3, which is characterized in that the list of the carbon-carbon double bonds
Body E be selected from acrylamide, Methacrylamide, glycidyl methacrylate, allyl glycidyl ether, acryloyl chloride,
One or more of methacrylic chloride, methylacryoyloxyethyl isocyanates and its derivative.
5. the graft copolymer containing reactive group according to claim 3, which is characterized in that the height of the carbon-carbon double bonds
The number-average molecular weight of Molecularly Imprinted Polymer C is 3000 ~ 13000.
6. the graft copolymer according to claim 1 or claim 2 containing reactive group, which is characterized in that the carbon-carbon double bonds
Monomer A be selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate, propylene
Sour methyl esters, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, styrene, α-methylstyrene, α-ethyl styrene, third
It is one or more of in alkene nitrile, methacrylonitrile and its derivative.
7. the graft copolymer according to claim 1 or claim 2 containing reactive group, which is characterized in that described containing reactive base
The unsaturated monomer B of group is selected from unsaturated acid anhydride, carboxylic acid, isocyanates, hydroxy ester, amide, oxazolines, siloxanes and its derivative
One or more of object.
8. the graft copolymer according to claim 1 or claim 2 containing reactive group, which is characterized in that described containing reactive base
The viscous state temperature of the graft copolymer of group is 130 DEG C ~ 200 DEG C, preferably 140 DEG C ~ 180 DEG C.
9. the preparation method of the graft copolymer containing reactive group described in claim any one of 1-8, which is characterized in that including
Following steps：
By the high molecular polymer C of the monomer A of carbon-carbon double bonds, unsaturated monomer B and carbon-carbon double bonds containing reactive group
It is copolymerized by free radical polymerisation process；The free radical polymerisation process is bulk polymerization, polymerisation in solution, suspension polymerisation or breast
Liquid polymerize.
10. the preparation method of the graft copolymer containing reactive group according to claim 9, which is characterized in that described to contain
The preparation method of the high molecular polymer C of carbon-carbon double bond, includes the following steps：
Under the conditions of existing for chain-transferring agent, by one in styrene, α-methylstyrene, α-ethyl styrene and its derivative
Kind or several and methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate, propylene
One or more of sour methyl esters, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer cause radical polymerization by initiator
It closes and high molecular polymer D is made；Then obtained high molecular polymer D is reacted at room temperature with the monomer E of carbon-carbon double bonds,
Obtain the high molecular polymer C of carbon-carbon double bonds.
11. the preparation method of the graft copolymer containing reactive group according to claim 10, which is characterized in that the height
The molar ratio of Molecularly Imprinted Polymer D and the monomer E of carbon-carbon double bonds are 1:0.8~1.3.
12. the preparation method of the graft copolymer containing reactive group according to claim 10, which is characterized in that the chain
Transfer agent is one or more of the aliphatic mercaptan containing carboxyl, hydroxyl or amino；The initiator causes for azo
One or more of agent, peroxide initiator or redox initiator.
13. the graft copolymer containing reactive group described in claim any one of 1-8 improve glass fibre filling ABS material or
Application in the intensity of abs polymer alloy.
14. a kind of ABS resin composition, including the graft copolymerization containing reactive group described in any one of claim 1-8
Object and ABS resin.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256442A (en) * | 1993-03-04 | 1994-09-13 | Mitsubishi Petrochem Co Ltd | Production of graft copolymer |
| CN103421154A (en) * | 2013-07-25 | 2013-12-04 | 杭州师范大学 | Comb-shaped stem grafting copolymer containing reactive group and preparation method and application thereof |
| CN104610515A (en) * | 2014-12-24 | 2015-05-13 | 杭州师范大学 | Reactive group-contained comb-type graft copolymer, and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256442A (en) * | 1993-03-04 | 1994-09-13 | Mitsubishi Petrochem Co Ltd | Production of graft copolymer |
| CN103421154A (en) * | 2013-07-25 | 2013-12-04 | 杭州师范大学 | Comb-shaped stem grafting copolymer containing reactive group and preparation method and application thereof |
| CN104610515A (en) * | 2014-12-24 | 2015-05-13 | 杭州师范大学 | Reactive group-contained comb-type graft copolymer, and preparation method and application thereof |
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